Monoazo dyes containing a dihydroxyphenyl containing alpha-carbamylethoxy-1-naphthol moiety



United States Patent MONOAZO DYES CONTAKNING A DIHYDROXY- PHENYLCONTAINING a-CARBAMYLETHOXY- l-NAPHTHOL MOIETY Milton Green, Newton, andPhylis T. Moore, Lexington, Mass, assignors to Polaroid Corporation,Cambridge, Mass., a corporation of Delaware No Drawing. Originalapplication Mar. 4, 1963, Ser. No. 262,358. Divided and this applicationSept. 6, 1966, Ser. No. 594,297

11 Claims. (Cl. 260202) ABSTRACT OF THE DISCLOSURE Azo hydroxynaphthoxydyes including a dihydroxyphenyl silver halide developing radical in asubstituent bonded to the oxygen atom of the naphthoxy moiety useful assilver halide developing agents capable of developing an exposed silverhalide emulsion and imparting a reversed or positive image of thedeveloped image to a super-posed image-receiving material.

This application is a division of application Ser. No. 262,358 filedMar. 4, 1963, now U.S. Patent No. 3,297,441.

This invention relates to photography and more particularly to products,compositions and processes for the development of photo-sensitive silverhalide elements.

It is one object of the present invention to provide novel processes andcompositions for the development of silver halide emulsions, in whichnovel colored silver halide developing agents are used.

Another object is to provide novel processes and compositions for thedevelopment of silver halide emulsions, in which the novel silver halidedeveloping agent is capable of developing an exposed silver halideemulsion and imparting a reversed or positive colored image of thedeveloped image to a superposed image-receiving material.

Further objects are to provide said novel silver halide developingagents, and novel products, processes and compositions suitable for usein preparing monochromatic and multichromatic photographic images by theemployment of said novel silver halide developing agents.

Other objects of the invention will in part be obvious and will in partappear hereinafter.

The invention accordingly comprises the processes involving the severalsteps and the relation and order of one or more of such steps withrespect to each of the others, and the products and compositionspossessing the features, properties and the relation of elements whichare exemplified in the following detailed disclosure, and the scope ofthe application of which will be indicated in the claims.

U.S. Patent No. 2,983,606, issued May 9, 1961 to Howard G. Rogers,discloses diffusion transfer processes wherein a photographic negativematerial, such as a photographic element comprising an exposed silverhalide emulsion, is developed in the presence of a dye developer toimpart to an image-receiving layer a reversed or positive dye image ofthe developed image by permeating into said emulsion a suitable liquidprocessing composition and bringing said emulsion into superposedrelationship with an appropriate image-receiving layer. The inventiveconcepts herein set forth provide novel dye developers which may beadvantageously used in such processes.

The novel dye developers of this invention may be represented by thefollowing formula:

3,365,441 Patented Jan. 23, 1968 wherein Q is a dihydroxyphenyl silverhalide developing radical, e.g., p-dihydroxyphenyl, o-dihydroxypheny-l,and nuclear substituted derivatives thereof, e.g., alkyl and/or halogensubstituted derivatives; Z is phenylene, lower alkylene, or lowerphenalkylene; m is a positive integer from 1 to 2; R is a lower alkyleneradical; and Y is an azo dye radical; said O' substituent being bondeddirectly to a nuclear carbon atom of the azo dye radical, e.g., to anuclear carbon atom of an aromatic or heterocyclic snbstituent of thedye radical.

As examples of lower alkylene radicals which may be employed for said Zand/ or R substituents, mention may be made of methylene, ethylene,ethylidene, propylene, isopropylene, etc.

The novel dye developers of this invention my also contain an additionalsilver halide developing radical linked to the dye moiety of themolecule through an appropriate organic linking group.

One useful class of dye developers Within the scope of Formula A may bedefined as azonaphthol dye developers wherein the --O substituent isbonded directly to the naphthalene nucleus in a position meta to the azolinkage.

A preferred group are naphthol derivatives which may be represented bythe formula:

( )R( NH(Z)m1-'Q wherein W is the radical of a diazotizable amine,preferably of the benzene or naphthalene series and R, Z, In and Q havethe meanings heretofore noted.

As examples of diazotizable amines which may be employed to preparesubstituent W, mention may be made of the following compounds:

omco

o rn-o H:N In

C HaCOO p (1&2,5d1acet0xyphenethyl) aniline otrno 0 o o o H,o0-NH N n,

p-(5-2,5-dicathyloxy-phenylacetarnido) aniline p-Acetarnidoaniltnep-(2,fi-dlacetoxypllenylmethyl) aniline 3 4 (EHO; (G) (|)1I 11(Z-meth'oxy-S-methyl) aniline OH O l The following compounds arerepresent-ative of prea v Nu ferred dye developers within the scope ofthe above-men- 3 tioned formulae: 0 6

(I) H (l) H l O H (I) H H;

l C H:

O OlII 4 a [p (B 2",5"-dihydroxypl1enethyl)-phenylcarbamy1]-ethoxy-2-[p-(2",5 dlhydroxyphenylmethyl) phenylazo} CHaCI-I-CNHl-naphthol 5 (2) OH O CH; 6H

I 4-a-[p-(2",5-dihydr0xypheny1)-phenylcnrbumy1]-eth0xy-2- O(2,4.',6-tr1methyl)-phenylazo-1-naphth0l4-0,(2,5-dihydroxyphenylcarbnmyl)-ethoxy2- (2-methoxy)- 0 Rphenylaz0-1-naphth0l I4-0,-[p-(2",5-dlhydroxypheny1)phenylcarbamyl]-ethoxy-2-p-n1ethylphenylazo-l-naphthol H O H O O OH am 4m 0 omoflt Nr-lomoni OHThe following compounds are illustrative of other use- -a-[p(6-2',5-dil1ydr0xyplicnethyl)-phenylcarbamyl]- Gummy"?(phomogentisammo)phenymzo l naphthol ful dye developers within the scope of the presentinvention: O H (l) H N=N/CH2C H,

I OH t1 0 0 H I 0 o1n01r-c-Nn-onzom- I ll GH:CHCNH- 0 I ll et-a-[p-(B-2",5 '-dlhydroxyphenethyl) -phenylcarbamyl]- eth0xy-2- (2'-methoxy) -phenylazo-1-naphth0l 4-a- [p- (B2",5"-dihydroxyphenethyl)phenylcarbamyl] ethoxy-2- p-acetamido) -phenylazo-1-naphthol (13) (I) H0 Ha It will be noted that the preferred group of dye developers ofFormula B, as illustrated by the aforementioned 13 specific compounds,have the developing moiety linked to the naphthol nucleus. The linkingof the developing moiety to the dye moiety according to the presentinvention afiords advantages not heretofore obtainable, since it permitsW of Formula B to be more readily substituted in a variety of positionsthan was heretofore possible when the developing moiety was linked tothis substituent. In addition to providing a class of dye developerswhich may be readily synthesized, the present invention makes itpossible to prepare a large class of dye developers which may containvarious substituents contributing to the sta bility, spectral absorptioncharacteristics, etc., of the compound. In other words, the presentinvention makes it possible to synthesize simply a large number of dyedevelopers having slightly different characteristics which may bedesired by the practitioner. This factor is particularly advantageous inmulticolor photography where a very exacting and delicate balance ofdyes is necessary to obtain a multicolor image having spectralabsorption characteristics closely approximating the original subjectmatter. By slight modifications or substitution of various substituents, one skilled in the art may modify the physical and/ oroptical characteristics of the dye developers of the present inventionto combine with the other dyes used in the system to obtain a multicolorimage having the desired characteristics of stability, color, etc.

The preferred compounds of Formula 1-9 have also been found, quiteunexpectedly, to possess increased stability to light over azonaphtholdye developers, such as 2 [p (fl 2',5 dihydroxyphenethyl) phenylazo] 4-isoproxy-l-naphthol, which are described in copending US. applicationSer. No. 144,816, filed Oct. 18, 1961, now US. Patent No. 3,134,672.When subjected to standard heat stability tests for 40 hours at atemperature of 120 F., the compounds of Formulae 1-9 showed little or nochange. When subjected to standard light stability tests with a xenonare for periods of 40 and hours, these compounds exhibited substantiallyincreased stability, showing appreciably less fading than did theaforementioned prior azo-naphthol dye developers.

The novel dye developers of this invention may be prepared by reacting acompound of the formula:

with a tertiary amine, e.g., trimethylamine, triethylarnine,tripropylamine, tributylamine, methylpiperidine, ethylpiperidine,dimethylaniline, etc., (trialkyl amines such as triethylarnine beingpreferred), to form the ammonium salt thereof; reacting this ammoniumsalt with an alkylchlorocarbamate, e.g., methyl, ethyl, isopropyl,isobutylchlorocarbonate, etc., to form a mixed anhydride of the formula:

and thereafter reacting the mixed anhydride of Formula D with an amineof the formula:

wherein Q is a dihydroxyphenyl silver halide developing radical or aprotected derivative thereof, to form the dye developers of Formula A.

In order to prevent disproportionation of the mixed anhydride of FormulaD, it is necessary to perform the final two reactions at a reducedtemperature at which disproportionation is precluded, e.g., at or below0 C., preferably at -5 C., and in an inert solvent which will not freezeat the particular temperature employed. As used herein, the term inertsolvent means a solvent or mixture of solvents which is chemically inertto or unreactive with the reactants or the reaction product. As examplesof such solvents, mention may be made of acetone, carbon tetrachloride,toluene, anisole, chloroform, etc.

While Q of Formula B may be a dihydroxyphenyl silver halide developingradical, Q is preferably a protected derivative thereof, since anyexcess of tertiary amine present in the reaction mixture will permitreaction of the unprotected hydroxy groups with the mixed anhydride toform an ester rather than the desired amide. It will be appreciated,however, that where care is exercised in avoiding an excess of tertiaryamine, it is not necessary to employ the protected derivatives. Asexamples of protected dihydroxyphenyl silver halide developing radicals,mention may be made of diacetoxyphenyl, dibenzyloxyphenyl, etc. Theprotective groups may be removed by hydrolysis in known manner to formthe desired dye developer.

The foregoing synthesis provides a particularly useful method forpreparing the preferred class of dye developers of Formula B. In thesame manner as described above, an azo dye of the formula:

is reacted with a tertiary amine to form the ammonium salt thereof; theammonium salt is then reacted with an 7 alkylchlorocarbonate to form amixed anhydride of the formula:

and the mixed anhydride is then reacted with an amine of Formula E toprovide the azo dye of Formula B. As was stated previously, if aprotected dihydroxyphenyl silver halide developing radical is employedin the synthesis, the azo dye must be hydrolyzed to remove theprotective groups.

In Formulae C to H, it will be appreciated that the symbolicdesignations for the various substituents have the meanings heretoforegiven with reference to Formulae A and B.

Compounds of Formula F and their synthesis are described and claimed incopending application Ser. No. 262,357 filed concurrently and now US.Patent No. 3,328,- 386; and compounds of Formula G and their synthesis,as well as the ammonium salt intermediates, are described and claimed inUS. Patent No. 3,256,269. Accordingly, these compounds and theirsynthesis comprise no part per se of the present invention.

The compounds of Formula E may be prepared in a manner similar to thatdisclosed in U.S. Patent No. 3,019,254, issued Jan. 30, 1962. Asexamples of such compounds, mention may be made of 2,5-diacetoxyphenylaniline; 2,5-diacetoxyaniline; 2,5-diacetoxyphenylmethyl aniline;fl-2,5-diacetoxyphenethyl aniline, etc.; including the correspondinganiline hydrochlorides.

Where the starting compounds of Formula C may be converted to their acidchloride without the necessity of employing elevated temperatures toform a solution of the reactants, the novel dye developers of thisinvention may also be prepared by the steps of first forming the acidchloride of the acid of Formula C and thereafter reacting the acidchloride with a compound of Formula E where Q is a protecteddihydroxyphenyl silver halide developing radical. Subsequent hydrolysisof the reaction product will yield the dye developer. Compounds 7 and10, for example, have been prepared by this alternative synthesis. Whereheat is necessary to form the solution, however, it has been found thatany hydroxyl radicals present in the dye molecule (e.g., the hydroxysubstituent on the naphthalene nucleus of the preferred compounds ofFormula B) are replaced by a chlorine atom.

The following examples show by way of illustration and not by way oflimitation the preparation of the novel compounds of this invention:

EXAMPLE I ot-(4-hydroxy)-1-naphthoxypropionic acid. 1,4-naphthoquinone(0.144 mole) and stannous chloride (0.144 mole, anhydrous) weredissolved at room temperature with stirring in 350 ml. of ethyl lactate.The solution was cooled to 10 C. and hydrogen chloride was bubbledthrough the solution at a brisk rate for six hours (the temperature ofsolution being held at 5-10 C.). The resultant clear reaction solutionwas poured into 750 ml. of a water-ice mixture. The oil which separatedupon standing was separated by decantation of the water phase. The oilyproduct was washed with a small volume of water then hydrolyzed.Nitrogen was bubbled through the water slurry for 1 hour with stirring.Nitrogen bubbling was continued while a solution of sodium hydroxide(.28 mole in 150 ml. of water which had been purged for 1 hour with Nwas added over a 5 min. period with stirring (at room temperature). Theresultant clear basic solution was stirred for an additional 15 min. andthen acidified (to a pH of 2) by the slow addition of 6 N hydrochloricacid (keeping a nitrogen atmosphere until the hydrolysis mixture wasacidic). The precipitate was dissolved in sodium bicarbonate solution,the insoluble impurities removed by filtration, and the product wasprecipitated from the filtrate by acidification with dilute hydrochloricacid. The product obtained had M.P. 154161' C. and was purified furtherby recrystallization from toluene to yielda-(4-hydroxy)-1-naphthoxypropionic acid, M.P. 157159 C., having thefollowing structural formula:

Elemental analysis of the product as C H O Found: C, 67.1; H, 5.2.Calculated: C, 67.2; H, 5.19.

EXAMPLE II 4 a-[p-(fl-2",5" dihydroxyphenethyl) phenylcarbamyl]-ethoxy 2[p (2",5-dihydroxyphenylmethyl) phenylazo] 1 naphthol (Compound 1).

p-(2,5 diacetoxyphenylmethyl) aniline hydrochloride (.015 mole) wasdiazotized with sodium nitrite (.015 mole) and hydrochloric acid (.030mole) in ml. water at 0-5", and the slight excess of nitrous acid wasdecomposed with sulfamic acid. The diazonium solution (0-5 was addedover a 10 minute period to a solution (at 10) of 0c(4-hydroxy-1-naphthoxy) propionic acid (.015 mole) in an acetone-watermixture containing sodium bicarbonate (excess). The reaction mixture wasacidified with dilute hydrochloric acid to dissolve the sodium salt ofthe dye acid (which had separated during the coupling) and toprecipitate the dye acid, ot-[3-p-(2',5- diacetoxyphenylmethyl)phenylazo 4 hydroxy-lnaphthoxy] propionic acid. A solution of the dyeacid (.0083 mole) in dry acetone (minimum volume) was deaerated withnitrogen and treated with trimethylamine (dry, .0083 mole). The acetonesolution of the triethylammonium salt of the dye acid was cooled to 5and isobutylchlorocarbonate (.0083 mole) was added. The reaction mixturewas stirred at -5 (in a nitrogen atmosphere) for an additional 25minutes. An acetone solution (dc-aerated and chilled) of p(fl-LS-diacetoxyphenethyl) aniline (.0083 mole) (which had beengenerated in solution from the hydrochloride by addition oftriethylamine (.0083 mole)) was added with stirring over a 15 minuteperiod to the acetone solution of the mixed anhydride at -5 (in anitrogen atmosphere). The cooling bath was removed and the reactionmixture was stirred overnight. The reaction mixture was filtered toremove some triethylamine hydrochloride, the precipitate washed withacetone and the filtrate and washings concentrated to dryness in vacuo.The glassy residue was washed with water and dilute acid. The solid wasdissolved in methyl Cellosolve (minimum volume) and the solution waspurged with nitrogen and cooled to 0 C. An oxygen-free aqueous solutionof sodium hydroxide (.050 mole) was added and the solution stirred for 1hr. at 0 C. maintaining a nitrogen atmosphere. The solution wasacidified with dilute hydrochloric acid and the precipitate wasrecrystallized from a mixture of acetone and benzene yielding 4-0:[p-(fi-2",5"-dihydroxyphenethyl) phenylcarbamyl] ethoxy 2 [p-(2",5"-dihydroxyphenylmethyl) phenylazo] 1 naphthol, Ml. l94199 C., A of 522 mmethyl Cellosolve.

9 EXAMPLE III 4-a-(2',5' dihydroxyphenylcarbamyl) ethoxy-2-(2'-methoxy)-phenylazo-1-naphthol (Compound 2).

o-anisidine (.022 mole) was diazotized with sodium nitrite (.022 mole)and hydrochloric acid (.066 mole) in 50 ml. of water at to The cooleddiazonium solution was slowly added (over a ten minute period) to asolution of .020 mole of a(4 hydroxy-l-naphthoxy) propionic acid in anacetone-water mixture containing an excess of sodium bicarbonate. Thesodium salt of the dye acid which had precipitated from the couplingmixture was converted to the dye acid upon acidification of the couplingmixture with dilute'hydrochloric acid. The precipitated acid wasrecrystallized from methyl Cellosolve affording 0t [3(o-methoxyphenylazo)-4-hydroxyl-naphthoxy] propionic acid, M.P. 248249,in 90% yield. The purified and dried dye acid (.0145 mole) was dissolvedin dry chloroform (minimum volume) and triethylamine (dry, .0145 mole)was added. The chloroform solution of the triethylammonium salt of thedye acid was de-aerated by bubbling nitrogen through the solution andcooled to 2. Isobutylchlorocarbonate (.0145 mole) was added withstirring and the reaction mixture held at 2 to 0 (N atmosphere) for 25minutes whereupon the formation of the mixed anhydride was assumed to becomplete. An acetone solution (deaerated and chilled) ofZ-hydroxy-S-benzoxy-aniline (.016 mole) was added gradually to thestirred solution of the mixed anhydride. The temperature of the reactionmixture was held at -2 during this addition (ca. min.). The cooling bathwas then removed and the reaction mixture was stirred overnight (Natmosphere). The reaction mixture was filtered toremove sometriethylamine hydrochloride, the solid washed with acetone, and thefiltrate and washings combined. The solution was concentrated to dryness(in vacuo) and the glassy residue washed with water and dilute acid. Theproduct solidified; it was collected on a filter and dried in vacuo. Thesolid was dissolved in methyl Cellosolve (minimum volume) and hydrolyzedin an N atmosphere as described in Example III. The dye developer afterrecrystallization from a methyl Cellosolve-H O mixture melted at254-256" C.

EXAMPLE IV 4 a [p (2,5" dihydroxyphenyl) phenylcarbamyl] ethoxy 2 (2methoxy-5-methyl)-phenylazol-naphthol (Compound 3) was prepared in amanner similar to that set forth in Example III, substituting 2-methoxy-S-methyl aniline for o-anisidine and p-hydroquinonyl aniline for2-1ydroxy-5-benzoxy aniline. The isolated dye developer melted at251-253 C., exhibited a k of 540 m in methyl Cellosolve and was found tobe soluble in chloroform, methylene chloride and alcohols.

EXAMPLE V 4 or. [p (B-2",5-dihydroxyphenethyl)-phenylcarbamyl] ethoxy 2(p homogentisamido)-phenylazol-naphthol (Compound 4) was prepared in amanner similar to that set forth in Example II substituting dicathyloxyhomogentisamido aniline hydrochloride for p (2, S-diacetoxyphenylmethyl)aniline hydrochloride. The isolated dye developer, 4-ot-[p-(B-2,5"dihydroxyphenethyl) phenylcarbamyl] ethoxy 2(p-homogentisamido)-phenylazo-1-naphthol, melted at 201-209 C.,exhibited a h of 532 mu in methyl Cellosolve and was found to be solublein acetone and 5% aqueous sodium hydroxide.

EXAMPLE VI 4 a [p (ti-2",5" dihydroxyphenethyl)-phenylcarbamyl] ethoxy 2[p-(,6-2",5"-dihydr0xyphenethyl)- phenylazo] 1 naphthol (Compound 5) wasprepared in a manner similar to that set forth in Example IIsubstituting p-((3-2,S-diacetoxyphenethyl) aniline hydro- 10 chloridefor p-(2,S-diacetoxyphenylmethyl) aniline hydrochloride. The product,4-04-[p-(fl-2",5"-dihydroxyphenethyl) phenylcarbamyl] ethoxy 2 [p 82,5"- dihydroxyphenethyl)-phenylazo] 1 naphthol, melted at 211-215 C.and exhibited a A of 525 mp. in methyl Cellosolve.

EXAMPLE VII 4-a-[p-(2",5" dihydroxyphenyl) phenylcarbamyl]-ethoxy-2-[p-( S-2",5"-dihydroxyphenethyl) phenylazo]- l-naphthol(Compound 6) was prepared in a manner similar to that set forth inExample II substituting p-(B- 2,5-diacetoxyphenethyl) anilinehydrochloride for 2,5-diacetoxy-phenethylmethyl aniline hydrochlorideand p-(B- 2,5-diacetoxyphenyl) aniline for p-(fl-2,5-diacetoxyphenethyl)aniline hydrochloride. The isolated dye developer,4-a-[p-(2,5"-dihydroxyphenyl) phenylcarbamyl] ethoxy-2-[p-(fl-2",5"dihydroxyphenethyl) phenylazo]-1- naphthol, melted at 136-141 C.,exhibited a A,,,,,,, of 525 m in methyl Cellosolve, and was found to besoluble in acetone, methanol and 5% sodium hydroxide.

EXAMPLE VIII 4-u-[p-(2",5" dihydroxyphenyl) phenylcarbamyl]-ethoxy-2-(2,4',6-trimethyl)-phenylazo-1-naphthol (Compound 7) wasprepared in a manner similar to that set forth in Example III,substituting mesidine for o-anisidine and p-hydroquinonyl aniline forZ-hydroxy-S-benzoxy aniline. The isolated dyed eveloper,4-a-[p-(2,5"-dihydroxyphenyl)-phenylcarbamyl] ethoxy 2(2',4',6-trimethyl)-phenylazo-1-naphthol, melted at 129-134 C.,exhibited a a of 520 my. in methyl Cellosolve, and was found to besoluble in acetone, ethanol and chloroform.

EXAMPLE IX 4-u-[p-(2,5" dihydroxyphenyl) phenylcarbamyl]-ethoxy-Z-p-methylphenylazo-l-naphthol (Compound 8) was prepared in amanner similar to that set forth in Example III, substituting ap-toluidine for o-anisidine and phydroquinonyl aniline for2-hydroxy-5-benzoxy aniline. The isolated dye developer,4-a-[p-(2",5"-dihydroxyphenyl)-phenylcarbamyl]-ethoxy 2 pmethylphenylazo-lnaphthol, melted at 261-262 C. and exhibited a A of 525my. in methyl Cellosolve.

EXAMPLE X 4-a-[p-(fl-Z",5"-dihydroxyphenethyl) phenylcarbamyl]-ethoxy 2[2' (N butyl)-carbamyl]-phenylazo-1- naphthol (Compound 9) was preparedin a manner similar to that set forth in Example III. In lieu of using0- anisidine, methyl anthranilate was diazotized and coupled witha-(4-hydroxyl-naphthoxy) propionic acid. The resulting dye,ot-(3-o-carbomethoxyphenylazo-4-hydroxy-1- naphthoxy) propionic acid,was then reacted with nbutylamine and the mixed anhydride of theresulting product was formed in the manner illustrated in Example III.The dye developer was prepared from the mixed anhydride by substitutingS-hydroquinonylethyl aniline for 2-hydroxy-S-benzoxy aniline, accordingto the procedure of Example 111. The isolated dye developer,4-a-[p-(B-2",5"- dihydroxyphenethyl) phenylcarbamyl]-ethoxy-2-[2'-(N-butyD-carbamyl]-phenylazo-1-naphthol, melted at 156- 164 C. andexhibited a A of 515 me in alcohol.

EXAMPLE XI 4-ix-(2,5-dihydroxyphenylcarbamyl)-ethoxy 2 (2-chloro-4-methyl)-phenylazo-1-naphthol (Compound 10) was prepared in amanner similar to that set forth in Example III, substituting2-chloro-4-methy1 aniline for oanisidine, The product,4-a-(2',5-dihydroxyphenylcarbamyl)-ethoxy-2-(2'-chloro 4' methyl)phenylazo-lnaphthol, melted at 237-240" 0., exhibited a A of 520 nm inmethyl Cellosolve, and was found to be soluble in ethanol.

1 1 EXAMPLE xrr 4-u-[p-( 3-2,5-dihydroxyphenethyl)phenylcarbamyl]-ethoxy-2-(2'-methoxy) phenylazo-l-na-phthol (Compound11) was prepared in a manner similar to that set forth in Example III,substituting S-hydroquinonylethyl aniline for2-hydroxy-5-benzoxyaniline. The isolated dye developer,4-u-[p-(5-2,5"-dihydroxyphenethy1)-phenylcarbamyl]-ethoxy-2-(2 methoxy)phenylazo-l-naphthol, melted at l33l36 C., and was soluble in methylCellosolve and aqueous sodium hydroxide.

EXAMPLE XIII 4-u-[p-(,B-2",5"-dihydroxyphenethyl) phenylcarbarnyl]-ethoxy-2- (p-acetamido -phenylazo-l-naphtho1 (Compound 12) was preparedin a manner similar to that set forth in Example III by usingp-acetamidoaniline in place of o-anisidine and S-hydroquinonylethylaniline in place of 2-hydroxy-5-benzoxy aniline. The resulting product,4-u-[p-(fi-2,5"-dihydroxyphenethyl)phenylcarbamyl]-ethxy-2-(p-acetamido)-phenylazo 1 naphthol, melted at244 0, exhibited a k of 531 111,11. in methyl Cellosolve, and wassoluble in acetone and dilute aqueous sodium hydroxide.

EXAMPLE XIV EXAMPLE XV A photosensitive element was prepared by coatinga gelatin subcoated film base at a speed of 10 feet/minute with asolution comprising 0.43 g. of 4-a-[p-(;8 2,5-dihydroxyphenethyl)phenylcarbamyl] ethoxy-2-[p-(2, 5 "-dihydroxyphenylmethyl)-phenylazo]-1-naphth0l (Formula 1) dissolved in cc. of 2% cellulose acetatehydrogen phthalate in a 50:50 mixture, by volume, of acetone andtetrahydrofuran. After this coating dried, a greensensitive silveriodobromide emulsion was coated on at a speed of 5 feet/minute andallowed to dry. This photosensitive element was exposed for 2 secondsand processed by spreading, between the thus exposed photosensitiveelement and a, superposed image-receiving element, an aqueous processingcomposition comprising:

Water cc 100 NaOH g 5.17 Hydroxyethyl cellulose (high viscosity)[commercially available from Hercules Powder Co., under the trade nameof Natrasol 250] g 4.0 Benzotriazole g 2.3 Sodium thiosulfate g 1.15N-benzyl-a-picolinium bromide g 2.3

The image-receiving element comprised a 2:1 mixture, by weight, ofpolyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support.After an imbibition period of approximately one minute, theimage-receiving element was separated and contained a magenta positiveimage.

EXAMPLE XVI The procedure described in Example XV was repeated, exceptthat the dye developer was dispersed in a layer of gelatin. The coatingsolution from which the dye developer was coated was prepared by adding0.75 g. of the dye developer dissolved in 1 cc. of cyclohexanone and 5cc. of di(tetrahydrofurfuryl)adipate. This mixture was agitated in aWaring Blendor for one minute with a solution of 5 g. of 10% gelatinsolution, 1.33 cc. of water, and 1 cc. of Alkanol B. After washing withwater, 5 cc. of the resulting dye dispersion was added to 10 cc. ofWater containing .75 cc. of saponin and two drops of succinaldehyde, andthen coated on the gelatin subcoated film base at a speed of 10feet/minute. Exposure and processing in the manner described in ExampleXV yielded a magenta positive image having a d 2.50 and a d of 0.50.

Since certain changes may be made in the above products, compositionsand processes without departing from the scope of the invention hereininvolved, it is intended that all matter contained in the abovedescription shall be interpreted as illustrative and not in a limitingsense.

What is claimed is:

1. A20 dyes of the formula:

0 Q-(Z)m1-NH-i )R0Y wherein Q is p-dihydroxyphenyl; Z is a memberselected from the group consisting of phenylene, lower alkylene andlower phenalkylene radicals; R is lower alkylene; m is a positiveinteger from 1 to 2, inclusive; and Y is the radical of a dye of thebenzeneazonaphthol series, said O substituent being bonded directly to anuclear carbon atom of the naphthol moiety of said dye.

2. A20 dyes of the formula:

wherein Q is p-dihydroxyphenyl; Z is a member selected from the groupconsisting of phenylene, lower alkylene and lower phenalkylene radicals;R is lower alkylene; m is a positive integer from 1 to 2, inclusive; andW is the radical of a diazotizable amine of the benzene series.

3. 4 on [p (p-2",5"'dihydroxyphenethyl)-phenylcarbamyl] ethoxy 2[p-(2",5"-dihydroxyphenylmethyl)- phenylaz01-1-naphthol.

4. 4 oc (2',5' dihydroxyphenylcarbamyl)-ethoxy 2-(2'-methoxy)-phenylazo-1-naphthol.

5. 4 u [p (2,5" dihydroxyphenyl) phenylcarbamyl] ethoxy 2 (2' methoxy 5'methyl) phenylazo-l-naphthol.

6. 4 or [p-(ii-2",5"-dihydroxyphenethyl)-phenylcarbamyl] ethoxy 2 (phomogentisamido) phenylazol-naphthol.

7. 4 or [p (B 2",5" dihydroxyphenethyl) phenylcarbamyl] ethoxy 2 [p ([32",5 dihydroxyphenethyl) -phenylazo]-1-naphthol.

8. 4 on [p (2",5 dihydroxyphenyl) pheny1carbamyl] ethoxy 2 [p (fl 2",5dihydroxyphenethyl)-phenylazo]-1-naphthol.

9. 4 a [p (2",5 dihydroxyphenyl) phenylcarbamyl] ethoxy 2 (2',4',6'trimethyl) phenylazo 1- naphthol.

1.0. 4 a [p (2",5" dihydroxyphenyl) phenylcarbamyl] ethoxy 2 pmethylphenylazo 1 -naphthol.

11. 4 a [p (f3 2",5 dihydroxyphenethyl) phenylcarbamyl] ethoxy 2 [2 (Nbutyl) carbamylI- phenylazo-l-naphthol.

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